Halogen substituted acylamino sulphonic acids of the aromatic series and their manufacture



PatentedNov. 21 J nALooEN SUBSTITUTED ACYLAMINO sunrnomc ACIDS OF THE AROMATIO SERIES AND THEIR MANUFACTURE Henry Martin, Basel,

Hans Heinrich Zaeslin,

Riehen, near Basel, and Rudolf Hirt, Curt Glatthaar, and Alfred Staub, Basel, Switzerland, minors to J. R. Geigy A. G., Basel,

Switzerland No Drawing. Application June 15, 1942, Serial No. 447,181. In Switzerland June 1c, 1938 4 Claims. (or. 260-500) This application is a continuation-impart of application Ser. No. 278,954, filed June 13, 1939 (now U. S. Patent No. 2,311,062).

This invention relates to the production of halogen substituted acyl amino sulphcnic acids, the products being useful for various purposes in industry e. g. for protecting wool and other substances against damage by moths, the protection being very fast to washing and fulling.

According to the present invention halogen substituted acyl amino sulphonic acids of the aromatic series are produced by the treatment of 1-amino-3 :4-dichlorobenzene 6 sulphonic acid with a halogen substituted phenyl carbamic acid halide Or a corresponding phenylisocyanate. Other methods for the manufacture of unsymmetrical diphenylureas are also suitable.

The herein claimed unsymmetrical halogensubstituted diphenylureasulfonic acids are colorless compounds which, in the form of their alkali salts, are well soluble in water. They are predominantly suitable for protecting, according to the acid dyeing methods, wool, feathers, furs, hair, paper, textiles, leather, natural or artificial fibres or articles containing these substances from moths and other textile destructive grubs. The pronounced fastness to washing and fulling of th products claimed is particularly worth mentioning.

The following examples illustrate the process, the parts being by weight, where nothing else is said.

. Example 1 12 parts of 1-amino-3z4-dichlorobenzene-6- sulphonic acid are dissolved in 75 parts by volume of dry pyridine. Then whilst stirring there are I introduced at -15 C. in small portions, 15

parts of 3:4-dichlorophenyl carbamic acid chloride or the corresponding quantity of the bromide or of 3 :4-dichlorophenylisocyanate and the whole is stirred for 1 hour at 40-50 C. -When no further free amine is traceable, the reaction mixture is treated with soda solution and the reaction mixture is then treated with steam until no further pyridine passes over. The residue is boiled with water, filtered and treated with a little cooking salt solution. The condensation product, the N-3:4-dich1oro-6-sulphopheny1-N'- 3':4'-dichlorophenyl urea is obtained in beautiful colorless laminae which, after washing and drying in vacuo, give the following analysis:

FoundCl:31.67%, S:'I.06%. Yield very good. CalculatedCl:31.5%, S:'7.08%.

Example 2 Into 500 parts of acetic acid ester which contain 135 parts of phosgene. there is slowly dropped a solution or 196 parts of 3:4:5-trichlor- 0 aniline in 1000 parts of acetic acid ester while simultaneously passing therethrough a current of phosgene. After the reaction is achieved, the solvent is distilled off in vacuo at 30 0., whereby the formed 3:4:fi-trichlorophenylcarbamic acid chloride remains as bright powder.

12.2 parts of the 1-amino-3z4-dichlorobenzene- 6-sulphom'c acid are dissolved in 100 part by volume of dry pyridine. While stirring there are introduced at room temperature by small por- 15 tions calculated quantities of the 3:4:5-trichlorophenylcarbamic acid chloride and the whole is stirred during one hour at 60 C. Whenon more free amine is detectable, after mixing with a soda solution the pyridine is blown oil by means of steam. The residue is boiled with water up to solution, filtered and mixed with a little common salt solution. The product of condensation, the sodium salt of the 3:4:3z4:5-pentachlorodiphenyl-urea-6-sulphonic acid is thus obtained in form of beautiful leaves. It is well soluble in warm water.

Example 3 Into 500 parts of acetic acid ester, which contain 135 parts of phosgene there is slowly dropped a solution of 196 parts of 2:4:5-trichloraniline in 1000 parts of acetic acid ester while simultaneously passing therethrough a current or phosgene.

' After the reaction is achieved, the solvent is distilled off warm, whereby the formed 2:4:5-trichlorophenylcarbamic acid chloride is converted under splitting oil of hydrochloric acid into the 2:4:5-trlchlorophenylisocyanate. 12.2 parts of l-amino-3z4-dichlorobenzene 6 sulphonic acid 40 are suspended in dry nitrobenzene and mixed while stirring at 1015 C. by portions with the equivalent quantity of 2:4:5-trichlorophenylisocyanate. Then stirring is continued at room temperature, until no free amino group is detectable. The product is then mixed with a soda solution and the nitrobenzen is blown off by means of steam. The residue is dissolved in hot water, then there is filtered and the product of reaction is precipitated by means of common salt as grey resin. After some time, the same crystallizes in form of a solid mass which crystallizes out from dilute alcohol in form of, small leaves.

Example 4 12.2 parts of 1-amino-3:4-dichlorobenzene-6- sulphonic acid are suspended in 200 parts byvolume of dry nitrobenzene and intermixed at 25- 30 C. with the calculated quantity of 4-chlorobenzoylazide, which is obtainable as usual by p-chlorobenzoylation of sodium azide and is'dis- Cl NH.CO.NH.Bz

wherein Bz means ahalogensubstituted aromatic radical of the benzene series, being in the form being, in the form ofthe sodium salt, beautiful colorless laminae, soluble in water, useful for durably protecting wool against moths.

3. The 3:4:3'z425' pentachlorodiphenylureafi-sulphonic acid of the following formula 01 w 01 CIQNELOONHQCI on! 1 being, in the form of the sodium salt, beautiful small plates, soluble in'water, useful for durably protecting wool against moths.

4. The 3:4:2:4:5' pentachlorodiphenylurea- B-sulphonic acid of the following formula 01 01 OFQNECONHQCI v olH 1 being, in the form of the sodium salt, beautiful small plates, soluble in water, useful for durably of-the sodium salts colorless compounds soluble protecting wool against moths.

in water, these compounds being useful for durably protecting wool and other substances against moths. 2. The 3:4:3'z4' tetrachlorodiphenylurea 6- sulphonic acid of the following formula 01 Cl v NECQMO-Cl 

